Carbohydrate foaming agent and process for its preparation



CARBOHYDRATE FOAMING AGENT AND PRGCESS FOR ITS PREPARATION William Schoen, Laurel, Miss, assignor to Masonite Corporation, Laurel, Miss, a corporation of Delaware No Drawing. Application June 11, 1952,

Serial No. 292,982

7 Claims. (Cl. 127-37) The present application is a continuation-in-part of application Serial No. 136,396 of the same applicant filed December 31, 1949 and now abandoned. This invention relates to a carbohydrate derivative, and relates more particularly to a water-insoluble composition of matter derived from a lignocellulose carbohydrate mixture. The invention relates to the novel composition of matter, to its method of manufacture, and to the uses in which the composition may be employed. The novel product of the present invention may be used, for example, in preparing low density fiuffy distended articles from fibrous materials such as kraft pulp and the like. The product may also be employed as a dispersion agent in conjunction with cements, clays, carbon black, and the like finely divided materials susceptible to dispersion in aqueous media. The novel composition of matter of the present invention is therefore most aptly described as a foamproducing, dispersion agent.

The product of the invention is obtained from the carbohydrate mixture resulting from the thermal hydrolysis of lignocellulose materials. The thermal hydrolysis of lignocellulose may be carried out in any one of several manners such as by subjecting wood of trees and woody materials of corn stalks, cane, and other vegetable growth-s to the action of steam under elevated temperatures and pressures. The carbohydrate mixture may also be obtained by acid hydrolysis of lignocellulose as well as by saccharification of wood. Preferably, however, the thermal hydrolysis is carried out by charging wood chips to a closed chamber (e; g. a gun as set forth in U. S. Patent No. 1,824,221 granted to William H. Mason on September 22, 1931), subjecting the chips to pressure of about 200-1200 pounds per square inch and a temperature of about 200300 C. for approximately 30 minutes to seconds, respectively, in the presence of steam, and then discharging the woody material from the gun through a constricted discharge means therein into a zone of lower pressure, preferably atmospheric pressure, thereby exploding the wood chips into comparatively finely divided elongated fibers and bundles of fibers. The gun conditions may be varied so as to be suited to changes in kind of Wood, size of chips (desirably up to about 1'' long), water content of the chips (preferably about 25%), extent of desired steam treatment, and the like. Under this treatment the wood undergoes hydrolysis, and water-insoluble and readily-hydrolyzable constituents thereof are rendered soluble or dispersible or suspendible in water.

In the hardboard making industry the greater portion of these water solubles is removed from the fiber before making it into boards. Removal may be accomplished by squeezing the fiber with rolls and/ or screws and the like apparatus or by washing the fiber in water. To wash the fiber it is passed into a tank and slurried with water and then delivered to and processed by'a washer (preferably a counter-current washer) thereby extracting the water solubles to such extent that the extract obtained ordinarily contains about 8%. of. waterzsolubles. .A.

tates Patent 0 smaller part of the water solubles remains in the washed fiber used for making into boards or the like. By evaporating water from the extract its content of water solubles can be increased or dried.

The hemicellulose fraction of wood, being made up of high molecular weight hexosans and pentosans and comprising some 20% of the original woody tissue, in large part gives rise to the water solubles and is believed to undergo the greatest change during the thermohydrolytic process described above. It is believed this hydrolysis effects a moderate reduction in the molecular weight of the hexosan and pentosan units in producing hexosan and pentosan units soluble in water. These units, plus a small amount of lignin, non-sugar carbohydrates, and gums make up the bulk of the constituents of the water solubles.

Water solubles resulting from such hydrolysis of lignocellulose materials as a class are applicable to this invention. A typical analysis of the water solubles made from pine wood and useful in this invention is given in the following table.

TABLE 1 Constituents of water solubles [Bone dry basis] The constituents of the water solubles will vary somewhat depending on the type lignocellulose material hydrolyzed and the conditions, e. g. time, temperature, pressure, etc., under which the lignocellulose material is hydrolyzed. Depending upon the above conditions, the constituents of the water solubles can vary roughly as shown in the following table:

TABLE 2 Constituents of water svlnbles [Bone dry basis] Constituents: Parts by weight Pentosans and hexosans 6080 Lignin 5-25 Non-sugar carbohydrates 5l5 I Gums 28 Although the water solubles may be used in the form recovered in practicing this invention, preferably they are concentrated by the evaporation of moisture before using. Concentrations of about by weight solids content have been found to produce a very satisfactory material. Optionally, water solubles in the form of a substantially dry powder may be used by redissolving in water to the desired concentration before use. These water solubles are sold in aqueous solution and in powder form under the trade marks Masonex and Masonoid, respectively. The term water solubles as used in the claims includes either form. Since for the purposes of this invention Masonex and Masonoid are equivalents, generally only Masonex will be referred to herein as a matter of convenience.

From the above description it will be seen that the major proportion of the water solubles consists of carbohydrate material. A more detailed analysis of the water solubles has indicated that the carbohydrate mixture is composed of oligosaccharides consisting of mannose, arabinose, glucose, galactose, and xylose sugar units. The .crude water solubles from which relatively all of the suspended material has been removed consists almost entirely of the above described oligosaccharide mixture. There is a relatively small fraction present, about 515% thereof, of monosaccharides. A larger fraction of the dissolved solids, i. e. about 50% thereof, consists of hexose and pentose oligosaccharides capable of conversion to the corresponding monosaccharides which are predominantly those named above. The remainder of the dissolved solids has been found to consist of polysaccharides having more than about 6 sugar units of the same 5 and 6 carbon atom character. in most instances, the filtered water solubles contain only from about 3 to about 6% of lignin.

The copending application of Robert M. Boehrn, entitled Process of Making Fibrous Articles, Serial No. 73,674, filed January 29, 1949, and now abandoned, discloses and claims a process of preparing flutfy low density cellular fibrous articles (e. g. sheets) by dispersing fibrous material with Masonex as the foaming agent, and then drying the fiber in the dispersed state. While good and useful articles result from the practice of said process, some difiiculties have been encountered. In drying the sheet there is a tendency for it to stick to the retaining member, e. g. a wire screen, on which the sheet may rest while being dried. This difficulty can be lessened somewhat by lubricating the wire screen but this practice is not entirely satisfactory. Another difliculty is that there is a tendency for a thin crust to form on the surface of the sheet during the drying step of said process. The foaming agent prepared according to the process of the present invention substantially eliminates these difficulties. Another advantage of the present invention is that materially less of this foaming agent than of Masonex is re quired to form a good article.

It has now been found that a greatly improved foaming and dispersion agent can be prepared by heating an aqueous solution of the above described water soluble material in a closed vessel at elevated temperature and pressure in the presence of an alkali metal hydroxide. More specifically, outstanding results have been obtained in preparing the novel product of this invention by heating an aqueous solution of the water solubles and an alkali metal hydroxide to a'temperature of about 140 C.- 220 C. and to a pressure of about 60-1000 pounds per square inch, further heating said mixture for about 5-60 minutes at about said temperature during which time the pressure increases to approximately 100-1100 pounds per square inch, and finally recovering the precipitated material which comprises the product of the present invention. In preparing the product of the invention on a large scale, e. g. on a production scale, it has been found necessary to stir the mixture during the heating in order to obtain good heat transfer.

When dried, as by spray drying or ordinary oven drving, the product is a brown powder, relatively free flowing, and non-hygroscopic in nature. It is characterized by a softening point within the range of about 180 C. to about 225 C. The product is completely soluble in organic solvents of the glycol type, including substituted glycols such as methyl Cellosolve, methyl Carbitol, and ethylene glycol. It is also soluble in pyridine as well as in aqueous alkali metal hydroxide. The product is slightly soluble in lower aliphatic alcohols and in acetone, dioxane, and ethyl acetate. It is insoluble in water, toluene, xylene, carbon tetrachloride, benzene, ethyl ether, chloroform, and the like organic solvents. Since the composition consists of a mixture of organic materials, it has been found to be impossible to ascribe to it any definite structural formula. However, analysis of the composition has included determinations of its various constituents and it has been found that the novel composition has a carboxyl content which may range from about 3.8% to nearly 6%, a hydroxyl content of from about 5% to about 7% and a methoxyl content of about 2%. The

composition ordinarily has an ash content ranging from about 1.4% to about 2.4%. From previous analytical determinations made on carbohydrate mixtures it appears that each molecule of the novel composition may contain about 4 hydroxyl groups, one methoxyl group, and one carboxyl group. Based on these assumptions and data the average molecular weight of the composition has been calculated to be about 935. Other analyses have shown that the composition contains about 67% carbon, 5.4% hydrogen and 25.7% oxygen. These determinations have permitted an assumed derivation of a generic formula in which the novel composition appears to be about as follows:

(C5-7H5-601.5-1.7)n

In using the novel composition of this invention as a foaming agent in the preparation of low density fluffy distended articles from kraft pulp, preferably a material which aids in stabilizing the dispersed and foamed mixture is used in conjunction with'the foaming agent. However, useful articles can be made in the absence of a stabilizer. Examples of such stabilizers are aluminum sulfate (Al2(SO4)3.18I-I2O) and calcium hydroxide. When the novel composition is employed as a dispersion agent, it is merely mixed with the dry finely divided cement, clay, carbon black, or the like material, or it may be added to an aqueous alkaline slurry thereof. While, as hereinbefore pointed out, the agent of the present invention possesses the ability to appreciably lower the surface tension of water, the composition does not have outstanding wetting powers. For this reason, it is believed that its ability to disperse cement and the like materials is due to electrical repulsive forces. Whatever the mechanism may be, the composition has outstanding dispersion characteristics and these characteristics will be hereinafter pointed out in greater particularity.

The following examples, wherein quantities are by weight unless otherwise specified, illustrate specific embodiments of the invention. It is to be understood, however, that the examples are for purposes of illustration only and the invention is limited only by the scope of the appended claims.

EXAMPLE 1 300 parts Masonex of 55.7% (167 parts solids content) was mixed with 55.7 parts of 30% NaOH (16.7 parts solids content). The pH of the resulting mixture was 11.5. This mixture was placed in a closed vessel and heated to a temperature of 186 C. at which temperature the pressure was 235 p. s. i. The mixture Was further heated for 10 minutes at a temperature of 186 C.-188 C. at the end of which time the pressure was 365 p. s. i. The contents of the vessel were allowed to cool to room temperature. At this stage the pH of the contents was 4.4. These contents comprise a liquid and solid (precipitate) fraction. The resulting precipitate was filtered, washed with hot water and dried. The yield of precipitate was 29.1% based on the Masonex solids. A portion of this dry precipitate was mixed with 1% NaOH solution in the ratio of 3.19 parts precipitate to parts NaOH. The NaOH insoluble portion (.23 part or 7.2%) of this precipitate was separated by filtration from the NaOH soluble portion (foaming agent). A yield of 27.0% foaming agent (dry basis) was obtained based on the weight of the original Masonex solids.

Fibrous sheets having a density of approximately 1.5 pounds per cubic foot, were made according to the following procedure using this foaming agent. 1000 parts of a slurry of fiber in water was prepared by thoroughly stirring kraft fiber in water to a 3% fiber consistency. To this slurry were added 2.5 parts Al2(SO4)3.l8H2O, 1 part Ca(OH)2 plus 2.96 parts of the foaming agent dissolved in 100 parts of a 1% NaOH solution (i. e. 100 parts of the filtrate described in the above paragraph). The resulting mixture was aerated until its volume had increased about three-fold. The aerated mixture was allowed to drain 15 minutes in a sheet mold followed by EXAMPLE 2 300 parts Masonex of 55.7% (167 parts solids content) was mixed with 55.7 parts of 30% NaOH (16.7 parts solids content). The pH of the resulting mixture was 11.0. This mixture was placed in a closed vessel and heated to a temperature of 142 C. at which temperature the pressure was 61 p. s. i. The mixture was preheated, and column B shows the pressure of the mixture at the end' of the preheating step. Column C ShOWs the temperature at which the mixture was further heated, and column D shows the pressure at the end of the heating step. After the heating step the contents of the vessel were allowed to cool to room temperature and the pH determined. The resulting precipitate was filtered, washed with hot water and dried. The dry precipitate was mixed with 1% NaOH solution and the NaOH insoluble portion was separated by filtration from the NaOH soluble portion (foaming agent). The yields of precipitate and foaming agent as shown are on a dry basis and as percent by weight of the original Masonex solids.

Preheating Step Heating Step Percent pH of Mixture Time, Percent Percent precipitate Mms. Foaming Precipitate insoluble in Tempera- Pressure, Tempera- Pressure, Agent 1% Na OH Before After ture, C. P. S. I. tulo, C P. S. I. Heating Heating A B C D E F G H I .T

was further heated for 35 minutes at a temperature of EXAMPLE 5 142 C.146 C. at the end of which time the pressure was 94 p. s. i. The contents of the vessel were allowed to cool to room temperature. At this stage the pH of the contents was 5.0. The resulting precipitate was filtered, washed with hot water and dried. The yield of precipitate was 18.8% based on the Masonex solids. A portion of this dry precipitate was mixed with 1% NaOH solution and the NaOH insoluble portion (17.5%) was separated by filtration from the NaOH soluble portion (foaming agent). A yield of 15.5% foaming agent (dry basis) was obtained, based on the weight of the original Masonex solids.

Good fibrous sheets similar to those in Example 1 were made with the foaming agent thus prepared. Substantially the same procedure disclosed in Example 1 was followed in making the sheets, except that four parts of the foaming agent was used.

EXAMPLE 3 300 parts Masonex of 55.7% 167 parts solids content) was mixcd with 55.7 parts of NaOH (16.7 parts solids content). The pH of the resulting mixture was 11.0. This mixture was placed in a closed vessel and heated to a temperature of 219 C. at which temperature the pressure was 995 p. s. i. The mixture was further heated for minutes at a temperature of 217 C.-220 C. at the end of which time the pressure was 1095 p. s. i. The contents of the vessel were allowed to cool to room temperature. The pH of the contents at this time was 4.0. The resulting precipitate was filtered, washed with hot water and dried. The yield of precipitate was 37.6% based on the Masonex solids. A portion of this dry precipitate was mixed with 1% NaOH solution and the NaOH insoluble portion (37.1%) was separated by filtration from the NaOH soluble portion (foaming agent). A yield of 23.7% foaming agent (dry basis) was obtained, based on the weight of the original Masonex solids.

' EXAMPLE 4 300 parts Masonex of 55.7% (167 parts solids content) Was mixed with 55.7 parts of 30% NaOH (16.7 parts solids content). The resulting mixture was divided into several portions and placed in closed vessels and subjected to the conditions tabulated below. The same steps were carried out as in Example 1 but under various'conditions as to temperature, time and pressure. Column A shows the temperature to which the mixture Calcium carbonate and kaolin were dispersed with the novel composition of the present invention in the following manner. An aqueous 50% slurry, containing grams of the material to be dispersed, was prepared from each of the above materials. A Knapp-Monarch mixer was employed to obtain the heavy slurry. Standardized dilute solutions of the dispersing agents were added to the individual slurries from a buret. The end point was recognized by a sharp break in viscosity of the slurry. In the table below, the commercial dispersing agents employed for comparative purposes were metallic salts of lignin sulfonate compositions.

02100 -100 GRAMS (50% AQUEOUS SLURRY) Ooncen- Percent tration of Volume Agent Dispersing of Agent Used Agent Required, (Based on (G111. per ml. wt.

ml.) CaC 0 Agent 1 0. 100 0. 39 Agent 2 0. 100 4 0. 39 Composition of this invention. 0. 066 0.27

KAOLlN-IOO GRAMS (50% AQUEOUS SLURRY) Agent 1 0.0100 12 0.120

Agent 2 0. 00556 35 0. 195

Composition of this invention". 0. 00550 15 0. 084

EXAMPLE 6 The above procedure was repeated with a carbon black dispersion consisting of 40.0 grams of carbon and cc. of water. A noticeable break in viscosity again indi- In practicing this invention according to a preferred embodiment thereof Masonex of approximately 40%- 60% concentration is mixed with an alkali metal hydroxide, e. g. sodium hydroxide or potassium hydroxide, such that on a solids basis the amount of alkali metal hydroxide is about 10% by weight of the Masonex. The mixture is heated in a closed vessel (e. g. a pressure bomb) to a temperature of about 185 C. and to a pressure of about 235 pounds per square inch. The mixture is heated for an additional 10 minutes at approximately 185 C. during which time the pressure increases to about 365 pounds per square inch. The foaming agent, in the form of a precipitate, is recovered by filtration and then washed with hot water and dried.

An outstanding advantage of this invention is its simplicity. While heating the mixture the desiredpressure builds up rather rapidly as a result of the evolution of gases from the mixture, and the pH of the mixture changes, from an alkaline pH (about 11) to an acid pH (about 4). An acid pH is necessary in order to precipitate the foaming agent produced. Thus the present invention eliminates the costly step of adding an acid in order to precipitate the foaming agent. Another advantage of this invention is that comparatively high yields of foaming agent are obtained.

Various modifications may be made in practicing this invention without departing from the scope thereof. The pressure varies directly with the temperature and time. In general temperature and time are somewhat interchangeable, i. e. the result obtained at a low temperature and long period of time is comparable to the result obtaincd at a higher temperature for a lesser period of time. However the matter of economy is to be considered. While a good foaming agent can be obtained at 140 C. and below, the time involved is considerably longer than with higher temperatures, e. g. l80 C. Although a good foaming agent can be obtained at temperatures above 220 C. the yields are less because of the increasing amount of the precipitate rendered insoluble in sodium hydroxide at the higher temperatures.

The concentration of alkali metal hydroxide and Masonex as Well as the relative proportions of each are not critical and may be varied over a rather wide range. Masonex below about 30% solids is not economical to use, whereas above about 70% solids it is very diificult to handle. Masonex of about 55% solids and 10% by weight of Masonex. of alkali metal hydroxide (of 30% concentration) on a solids basis was found to be very satisfactory.

While particularly good results were obtained with sodium hydroxide, the other members of the class of alkali metal hydroxides are substantially equivalent to sodium hydroxide for use in practicing this invention.

As a matter of obtaining a more refined foaming agent, it is preferred to wash and dry the precipitate, but such purification is not essential. Good foamed products can also be made using, the unwashed and undried precipitate as a foaming agent.

As the above and other apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A water-insoluble composition of matter derived from a lignocellulose carbohydrate mixture obtained by hydrolyzing lignocellulose at a temperature of about 200-300 C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, said composition consisting essentially of about 67% carbon, 5% hydrogen, 25% oxygen, and a minor proportion, not exceeding about 2.5%, of inorganic material, said carbohydrate derivative having a softening point range of from about 180 C. to about 225 C., a methoxyl group content of about 2%, a hydroxyl group content of about 7%, and a carboxyl group content of about 5%, said composition being soluble in aqueous alkali metal hydroxide, pyridine, glycols, and substituted glycols, and said composition being characterized by surface tension reducing ability and foam-producing and dispersion properties, said water-insoluble compositions being produced by heating an aqueous solution of said carbohydrate mixture in the presence of an alkali metal hydroxide, at an initial pH of about 11, at a temperature of about -220 C. and at a pressureof about 60-1000 pounds per square inch for about 5-60 minutes.

2. Process of preparing a foaming agent from a material consisting essentially of the water-soluble and watersuspendible carbohydrate reaction product resulting from hydrolyzing lignocellulose materials at a temperature of about 200-300 C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, followed by water washing and filtering said hydrolyzed material to obtain said water-soluble and water-suspendible carbohydrate material, which process comprises heating an aqueous mixture of said reaction product and a sufficient quantity of an alkali metal hydroxide to produce a pH of about 11 to a temperature of about 140 C.-220 C. and to a pressure of about 60- 1000 pounds per square inch, further heating said mixture for about 5-60 minutes at about said temperature during which time the pressure increases to about 100-1100 pounds per square inch.

3. Process of preparing a foaming agent from a material consisting essentially of the Water-soluble and Watersuspendible carbohydrate reaction product resulting from hydrolyzing lignocellulose materials at a temperature of about 200"30O C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, followed by water washing and filtering said hydrolyzed material to obtain said water-soluble and water-suspendible carbohydrate material, which process comprises heating an aqueous mixture of said reaction product and a sufficient quantity of an alkali metal hydroxide to produce a pH of about 11 to a temperature of about C.- C. and to a pressure of about 215-305 pounds per square inch, further heating said mixture for about 5-60 minutes at about said temperature during which time the pressure increases to about 275- 550 pounds per square inch.

4. Process of preparing a foaming agent from a material consisting essentially of the water-soluble and watersuspendible carbohydrate reaction product resulting from hydrolyzing lignocellulose materials at a temperature of about 200-300 C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, followed by water washing and filtering said hydrolyzed material to obtain said watersoluble and water-suspendible carbohydrate material, which process comprises heating an aqueous mixture of said reaction product and sodium hydroxide, at an initial pH of about 11, to a temperature of about 170 C.- 185 C. and to a pressure of about 215-305 pounds per square inch, further heating said mixture for about 5-60 minutes at about said temperature during which time the pressure increases to about 275-550 pounds per square inch.

5. Process of preparing a foaming agent from a material consisting essentially of the water-soluble and watersuspendible carbohydrate reaction product resulting from hydrolyzing lignocellulose materials at a temperature of about 200-300 C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, followed by water washing and filtering said hydrolyzing material to obtain said watersoluble and water-suspendible carbohydrate material, which process comprises heating an aqueous mixture of said reaction product and an alkali metal hydroxide, at an initial pH of about 11, to a temperature of about 185 C. and to a pressure of about 235 pounds per square inch, further heating said mixture for about 10 minutes at about said temperature during which time the pressure increases to about 365 pounds per square inch.

6. Process of preparing a foaming agent from a material consisting essentially of the water-soluble and watersuspendible carbohydrate reaction product resulting from hydrolyzing lignocellulose materials at a temperature of about 200300 C. and a pressure of about 200-1200 pounds per square inch for about 30 minutes to about 5 seconds, respectively, foilowed by water washing and filtering said hydrolyzed material to obtain said Waer soluble and water-suspendible carbohydrate material, which process comprises heating an aqueous mixture of said reaction product and sodium hydroxide, at an initial pH of about 11, to a temperature of about 185 C. and to a pressure of about 235 pounds per square inch, further heating said mixture for about 10 minutes at about said temperature during which time the pressure increases to about 365 pounds per square inch.

7. A carbohydrate derivative characterized by surface tension reducing ability and foam-producing and dispersion properties obtained according to the process of claim 2.

References Cited in the file of this patent UNITED STATES PATENTS 1,851,822 Farber Mar. 29, 1932 2,073,616 Acree Mar. 16, 1937 2,221,779 Collings et al Nov. 19, 1940 2,247,204 Schorger June 24, 1941 2,247,209 Schorger June 24, 1941 2,319,951 Schorger May 25, 1943 2,431,163 Boehm et a1 Nov. 18, 1947 2,449,209 Farber Sept. 14, 1948 2,453,213 Farber NOV. 9, 1948 2,465,347 Boehm et a1 Mar. 29, 1949 2,505,304 Salvesen Apr. 25, 1950 2,505,457 Bird Apr. 25, 1950 FOREIGN PATENTS 565,774 Great Britain Nov. 28, 1944 

1. A WATER-INSOLBLE COMPOSITION OF MATTER DERIVED FROM A LIGNOCELLULOSE CARBOHYDRATE MIXTURE OBTAINED BY HYDROLYZING LIGNOCELLULOSE A A TEMPERATURE OF ABOUT 200*-300*C. AND A PRESSURE OF ABOUT 200-1200 POUNDS PER SQUARE INCH FOR ABOUT 30 MINUTES TO ABOUT 5 SECONDS, RESPECTIVELY, SAID COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 67% CARBON, 5% HYDROGEN, 25% OXYGEN, AND A MINOR PROPORTION, NOT EXCEEDING ABOUT 2.5%, OF INORGANIC MATERIAL, SAID CARBOHYDRATE DERIVATIVE HEATING A SOFTENING POINT RANGE OF FROM ABOUT 180*C. TO ABOUT 225*C., A METHOXYL GROUP CONTENT OF ABOUT 2%, A HYDROXYL GROUP CONTENT OF ABOUT 7%, AND A CARBOXYL GROUP CONTENT OF ABOUT 5%, SAID COMPOSITION BEING SOLUBLE IN AQUEOUS ALKALI METAL HYDROXIDE, PYRIDIEN, GLYCOLS, AND SUBSTITUTED GLYCOLS, AND SAID COMPOSITION BEING CHARACTERIZED BY SURFACE TENSION REDUCING ABILITY AND FOAM-PRODUCING AND DISPERSION PROPERTIES, SAID WATER-INSOLUBLE COMPOSITION BEING PRODUCED BY HEATING AN AQUEOUS SOLUTION OF SAID CARBOHYDRATE MIXTURE IN THE PRESENCE OF AN ALKALI METAL HYDROXIDE, AT AN INITIAL PH OF ABOUT 11, AT A TEMPERATURE OF ABOUT 140*-220*C. AND AT A PRESSURE OF ABOUT 60-1000 POUNDS PER SQUARE INCH FOR ABOUT 5-60 MINUTES. 